ARTICLE

pubs.acs.org/JPCA

Inhibition of Light-Induced Tautomerization of 7-Azaindole by

Phenol: Indications of Proton-Coupled Electron/Energy Transfer
Quenching
Moitrayee Mukherjee, Shreetama Karmakar, and Tapas Chakraborty*
Department of Physical Chemistry and Raman Centre for Atomic Molecular and Optical Sciences, Indian Association for the Cultivation
of Science, Jadavpur, Calcutta 700032, India

ABSTRACT: The photophysical behavior of a 1:1 complex between phenol and

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7-azaindole (7AI) has been investigated in methylcyclohexane solutions at tempera-

tures in the range of 27 to -50 °C. A linear Benesi-Hildebrand plot associated with
changes in absorbance of the complex with phenol concentration in the solutions
ensures 1:1 stoichiometry of the produced complex. Our estimate for the value of the
association constant (Ka) of the complex is ∼120 M-1 at 27 °C, and it is nearly twice
compared to that for 1:1 complex between 7AI and ethanol measured under the same
condition. The complexation results in dramatic quenching of the normal fluores-
cence of 7AI and the process is accelerated upon lowering of temperature. The
measured spectra show no indication that phenol promotes tautomerization of 7AI in the excited state. We have argued that the
hydrogen bonding between pyridinic N and phenolic O-H (N 3 3 3 O-H) is a vital structural factor responsible for quenching of
7AI fluorescence, and this idea has been corroborated by showing that under same condition the fluorescence of 7AI is enhanced in
the presence of anisole. As a plausible mechanism of quenching, we have invoked a proton-coupled electron transfer (PCET)
process between phenol and excited 7AI, which outweighs the competing tautomerization process. An analysis in terms of Remm-
Weller model reveals that the PCET process involving phenol and excited 7AI could be energetically favorable (ΔG0ET< 0). An
alternative mechanism, where quenching can occur via electronic energy transfer from the excited protonated 7AI to phenoxide ion,
following a proton transfer along the N 3 3 3 O-H hydrogen bond, is also discussed.

1. INTRODUCTION of the normal dimer can be recorded in ultraviolet by measuring

Hydrogen bonding is a vital molecular interaction that governs
the dynamics of energy dissipation of excited molecules in
condensed phases as well as in molecular complexes isolated in
the gas phase.1 In the past couple of decades, doubly hydrogen-
bonded complexes of 7-azaindole (7AI) have been subjected to
extensive investigations from the viewpoints of photophysical
interests, both in hydrocarbon solutions2-19 and in cold envir-
onment of supersonic jet expansion.20-32 On UV excitation to
the lowest excited state, the monomer and doubly hydrogen-
bonded dimer of this molecule decay via two radically different
photophysical pathways. While the monomer emits intense UV
fluorescence, the dimer undergoes a nonradiative transition
almost exclusively resulting in formation of a tautomeric config-
uration via exchange of two protons/H-atoms. According to the
mechanism suggested for the process, both moieties of the dimer
are tautomerized simultaneously and emit green fluorescence
from the excited tautomeric configuration. An apparent reason of
the overwhelming interests shown in studying the details of this
photophysical process is due to the notion that similar tautomer-
ization within the base pairs are responsible for mutagenesis in
DNA replications.33,34
In a hydrocarbon solution at room temperature, the transition
from the normal to tautomeric configuration of the homodimer
(7AI2) is found to be almost exclusive.3 No distinct fluorescence
the steady-state fluorescence spectrum and this is consistent with
the finding of the time-resolved studies, where an ultrafast
growth of the green tautomer fluorescence is observed.4,7 An
extensive degree of experimental as well as theoretical efforts has
been devoted to resolve the other pertinent issue, that is, whether
the double proton/H atom transfer occur in concerted or
stepwise manner.8 Temperature variation studies at low tem-
peratures revealed an apparently very small barrier (∼1.5 kcal/
mol) to tautomerization.3 However, the origin of the barrier does
not appear to be very obvious. Recently, by measuring fluores-
cence spectra in a series of aprotic liquids at different tempera-
tures, Catalan suggested that some properties of the media, for
example, solvent viscosity, volume cavity, and so forth, could be
responsible for the observed barrier.35 Very efficient tautomer-
ization of 7AI also occurs in 1:1 doubly hydrogen bonded
complexes with carboxylic acids.17,18 In this case, carboxylic acids
act as efficient catalysts. Because of higher natural acidity of the
carboxylic acids, strongly bound doubly H-bonded cyclic com-
plexes are produced, which are structurally similar to the homo-
dimer. In fact, the value of the association constant (Ka) of 1:1
Received: September 4, 2010
Revised: December 29, 2010
Published: February 17, 2011

r 2011 American Chemical Society 1830 dx.doi.org/10.1021/jp1084422 | J. Phys. Chem. A 2011, 115, 1830–1836
The Journal of Physical Chemistry A
complex with acetic acid in hydrocarbon solution at room
temperature has been found to be much larger (Ka = 1.8
104
M-1) compared to the homodimer (7AI2) formation (Ka = 2.2

103 M-1).18 Furthermore, no UV fluorescence from the normal
form of the 7AI-acetic acid complex has been detected, and the
tautomeric form of the complex is the only emitting species, as in
the case of homodimer.
On the other hand the protic solvents display a large variation
in tautomerization efficiency, which depends also on the nature
of the reaction medium. No green fluorescence has been
detected from pure aqueous solutions of 7AI.9,12 However, such
fluorescence does appear when water is finely dispersed in diethyl
ether or tetrahydrofuran,16 and under such conditions water has
been proposed to form 1:1 complexes. However, in the bulk
water, owing to presence of extensive H-bonded networks,
probability for identification of the 1:1 complex turns out to be
small. On the other hand, a highly red-shifted normal fluores-
cence (λmax ∼ 385 nm) is observed from the fully solvated
species in the excited state. To account for the red-shifted
emission, the possibility for exciplex formation has also been
suggested.9 On the other hand, under a supersonic jet expansion
condition, no green fluorescence from the 1:1 water complex is
observed, but occurrence of such emission from a complex
containing two water molecules (1:2 type) has been reported
very recently.36
In contrast to the behavior of the water complex, green
fluorescence has been observed from a neat alcohol solution of
7AI9 and also when the alcohols are diluted in hydrocarbon
solvents at room temperature.10,14 It has been suggested that a
significant extent of 1:1 complex is also present in neat alcohol
solutions because of their lower tendency toward self-aggrega-
tions. In dilute hydrocarbon solution, 1:1 nature of the complex
between methanol and 7AI was ascertained from Benesi-
Hildebrand plot.14 However, unlike the homodimer and/or 1:1
complexes with carboxylic acids, alcohol-assisted tautomeriza-
tion is much slower, and the complexes display distinct normal
emission in the ultraviolet with λmax at ∼350 nm.14 This spectral
behavior is consistent with the experimental estimate of a small
value of association constant (Ka = 50 M-1) and also from the
theoretical prediction for a geometry of the 1:1 complex in which
the H-bonds are much weaker compared to those in the
homodimer and 1:1 complex with acetic acid. Analyzing the rate
of tautomerization assisted by a series of alcohols having different
acid-base characters, Kwon et al.14 have shown recently that the
double proton/H-atom transfer rates are increased profoundly
with the acidic character of the alcohols, and this led the authors
to propose that 7AI tautomerization is triggered by the transfer of
a proton from alcohol to the pyridinic nitrogen atom along the
N 3 3 3 H-O hydrogen bond. Second, the tautomerization is
significantly slowed down on isotopic (O-H/O-D) substitu-
tion of methanol and that indicates that the proton transfer is the
rate limiting step in the process.
In the present paper, we report the photophysical behavior of a
1:1 complex of 7AI with phenol. The motivations of the study are
the following. First, although catalytic influence of various
aliphatic alcohols has been explored extensively, no study, to
our knowledge, has been reported until the date on the influence
of aromatic alcohols. The acid dissociation constant of phenol
(pKa ∼ 10) being several orders of magnitude larger compared
to, for example, ethanol (pKa ∼ 16), the catalytic effect of the
former is expected to be much larger. Second, the S1rS0
electronic excitation energy of isolated phenol is about 1700
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cm-1 larger compared to that of 7AI.22,37 Therefore, in an
isolated complex the electronic interaction between the two
molecular moieties could be small if 7AI is excited to lowest
available electronic energy level. However, in a hydrocarbon
solution at room temperature, because of spectral broadening
and structural flexibility in a supporting liquid medium, new
photophysical pathways could be evolved, which can compete
with the tautomerization dynamics in the excited state. The
results presented below show that such a competing deactivation
channel dominates over the tautomerization channel.
2. EXPERIMENT
7-Azaindole and phenol were purchased from Sigma-Aldrich
and purified further by vacuum sublimation before use. Anisole
was procured from Spectrochem Pvt. Ltd. and purified by
vacuum distillation. UV grade methylcyclohexane and ethanol
were also obtained from Spectrochem and used as supplied after
testing their purity by measuring fluorescence spectra. The
spectrum of pure methylcyclohexane recorded by exciting at
300 nm is displayed in Figure 4, trace 5. Except for the two
Raman bands, there is no other emission. The concentration of
the stock solution of phenol was 2 M, and it was added gradually
to the said 7AI solution to get its effective concentration in the
range of 3.33
10-3 to 3.33
10-2 M. To prepare the 7AI-
ethanol and 7AI-anisole complexes, pure ethanol and anisole
were added to the said 7AI solution. The electronic absorption
spectra of all the solutions were recorded using a Shimadzu UV-
2410 spectrometer and the fluorescence spectra of the same sets
of solutions were recorded using a Jobin Yvon FluoroMax-3
spectrofluorimeter after correcting with respect to instrument
response parameters. For measuring the spectra at low tempera-
tures (absorption as well as fluorescence), a home-built double-
walled quartz dewar was used. The space in between the two
walls of the dewar was evacuated continuously by a vacuum
pump. The sample was taken in a round quartz cell and inserted
into the dewar and cooled by regulated flow of liquid nitrogen
vapor. The temperature inside the cell was monitored and
controlled using a home-built temperature controller with an
accuracy of (1 °C.
3. RESULTS AND DISCUSSION
3a. Structure of the Complex. The fully optimized structure
corresponding to the most favored conformation (doubly hydro-
gen-bonded cyclic geometry) of the 7AI-phenol complex (1:1)
in the ground state is displayed in Figure 1A. The basis set
superposition error (BSSE)-corrected binding energy is 9.9 kcal/
mol, and it is smaller compared to the 1:1 complex with acetic
acid (Figure 1B), which is known to be a very effective catalyst for
tautomerization of 7AI in the excited state. The optimized
geometric parameters of the two complexes indicates that the
hydrogen bond lengths in the latter complex are much shorter
compared to those in the former, and this happens because the
O-H group of one phenol molecule cannot be packed properly
between the widely separated pyridinic N and pyrrolic N-H
groups of 7AI to form two strong hydrogen bonds.
3b. Electronic Absorption Spectra of 7AI-Phenol Com-
plex. The complex is easily produced upon mixing phenol and
7AI in a hydrocarbon solution. In Figure 2, we have shown the
changes of the longest wavelength segment of the S1rS0
absorption system of 7AI in a dilute methylcyclohexane owing
to a successive increase of phenol concentration in the solution.
dx.doi.org/10.1021/jp1084422 |J. Phys. Chem. A 2011, 115, 1830–1836
The Journal of Physical Chemistry A
Figure 1. Optimized structures of (A) 7AI-phenol and (B) 7AI-acetic
acid complexes predicted by calculation at the DFT/B3LYP/6-311þ
G** level. The hydrogen bond lengths (Å) in complex A is predicted to
be longer compared to those in complex B.
Figure 2. Changes in the longest wavelength segment of S1rS0
absorption spectrum of 7AI upon complexation with phenol (PhOH)
in methylcyclohexane at room temperature. The traces 1-4 denote the
spectra recorded for 7AI solution (10-5 M) with different concentration
of phenol as mentioned in the figure. The longest wavelength segments
of the spectra of pure phenol solutions for the lowest and highest
concentrations used are shown using dashed lines, traces 5 and 6,
respectively. The depicted absorption spectra of the mixed solutions
(traces 2-4) are obtained after subtracting the absorbance of pure
phenol solution from the recorded absorbance of the mixed solutions
over the wavelength range shown.
To avoid formation of 7AI homodimer and maximizing the
concentration of the mixed dimer (1:1 complex), the concentra-
tion of 7AI was kept low (10-5 M) and the added phenol
concentration in the final solution was varied in the range of
3.33
10-3 to 3.33
10-2 M. The longest wavelength absorp-
tion profiles of only PhOH solution corresponding to the lowest
(3.33
10-3 M) and highest (3.33
10-2 M) concentrations
used in the mixed solution are also displayed (traces 5 and 6,
respectively). The 1:1 nature of the complex is ascertained by
observing a linear Benesi-Hildebrand plot associated with
changes in the absorption of the complex at 304 nm with
increasing concentration of phenol (Figure 3A). A direct non-
linear plot, depicting the increase in absorbance of the complex
(Acomplex) with phenol concentration for probing at 304 nm is
presented in part B of the Figure 3. The association constant (Ka)
of the complex estimated by analyzing the nonlinear plot
following the eq 3 in ref 18 is 120 ( 15 M-1. Under the same
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Figure 3. Benesi-Hildebrand plot (part A) showing changes in
absorbance at 304 nm of the 7AI-phenol complex with an increase in
concentration of the phenol in the methylcyclohexane solution of 7AI
(10-5 M). The nonlinear plot showing the increase in absorbance of the
complex with phenol concentration is presented in part B. A more
accurate value of association constant (Ka) is estimated from the
nonlinear plot.
condition, the value of Ka estimated for 7AI-ethanol complex is
62 ( 5 M-1, and it is somewhat similar to what has been
estimated for the 7AI-methanol complex (50 M-1) in n-
heptane by Kwon et al.14 Evidently, the higher value of Ka for
the former case is because of higher acidity of phenol compared
to methanol or ethanol. Nevertheless, Ka of 7AI-phenol com-
plex is much smaller compared to Ka found for 1:1 complex with
acetic acid (∼2
104 M-1),14 and the difference is consistent
with the prediction of the electronic structure calculation that the
binding energy of 7AI-acetic acid complex (15.3 kcal/mol) is
larger compared to that of 7AI-phenol complex, and accord-
ingly, the hydrogen bond lengths in the former case are predicted
to be much shorter compared to those in the latter. Thus, with
respect to both the estimated thermodynamic parameter (Ka)
and theoretical predictions, the present system under study is a
loosely bound hydrogen-bonded complex.
3c. Complexation Effects on Fluorescence Spectra. To
investigate the catalytic effect of phenol on the excited-state
tautomerization of 7AI in 1:1 doubly hydrogen-bonded complex
configuration, we have measured a set of fluorescence spectra
with mixed solutions containing 7AI (10-5 M) and phenol of
different concentrations in the range of 3.33
10-3 to 3.33

10-2 M. Three such spectra are presented in Figure 4 (traces 2-4)
along with that of the pure solution of 7AI (trace 1). All the
spectra are measured at room temperature by exciting at 300 nm.
dx.doi.org/10.1021/jp1084422 |J. Phys. Chem. A 2011, 115, 1830–1836
The Journal of Physical Chemistry A
It is worth mentioning that the sharp bands displayed on each of
the spectra at 312 and 324 nm are the Raman bands of the
solvent, because they show up in the same way in the emission
spectrum of pure methylcyclohexane (trace 5). The wavelength
positions of these bands undergo shifting with change in excita-
tion wavelength, which confirms the assignments, and the same
assignments were suggested also in earlier studies.17
Figure 4. Fluorescence spectra of 7AI in methylcyclohexane (10-5 M)
at room temperature in the presence of three different concentrations of
phenol (traces 1-4). The spectrum recorded in presence of ethanol of
concentration 2.85
10-2 M in the same 7AI solution is shown (trace
6) for a comparison. Excitation wavelength, λexc = 300 nm was kept fixed
to record all the emission spectra. The lowermost trace denotes the
emission spectrum of pure solvent. The sharp band at 324 nm is a Raman
band of the solvent. The fluorescence excitation spectra for the same set
of mixed and pure 7AI solutions are presented in the inset (traces 1-4).
The excitation spectra are recorded by probing the emission at 380 nm.
Figure 5. Fluorescence spectra recorded at six different temperatures (27 to -50 °C) of (A) mixed solution containing phenol (1.66
10-3 M) in the
10-5 M 7AI solution and (B) pure 7AI solution of same concentration. Excitation wavelength was 300 nm in recording all the spectra. The
corresponding excitation spectra recorded by probing tautomeric emission at 500 nm are shown in inset I and inset II respectively.
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Trace 1 indicates that at such low concentration of 7AI (10-5
M), the fluorescence of the pure solution appears almost
exclusively in the ultraviolet region, and it is emitted from the
locally excited state (S1) of the monomer. The concentration of
the dimer being low, the visible tautomer fluorescence, which is
emitted exclusively by this species, is also very small. Here the key
observation is that there is no indication for enhancement of
tautomer fluorescence with increase in phenol concentration in
the solutions; rather, the intensity of the UV fluorescence of the
monomer is sharply decreased. The monomer fluorescence
almost disappears when the phenol concentration is 3.33

10-2 M. In contrast, the trace 6 indicates that in the presence of
nearly the same concentration of ethanol, there is a significant
enhancement of tautomer fluorescence, and a distinct red-shifted
UV fluorescence with the maximum at ∼350 nm also appear.
The latter is the normal fluorescence of the 7AI-ethanol
complex, emitted from the locally excited state (S1).14 Thus,
the results presented here imply that although phenol is a
stronger proton donor compared to ethanol, it does not assist
in tautomerization of 7AI; rather it induces efficient deactivation
of 7AI exited state via some other nonradiative channels.
The fluorescence excitation spectra corresponding to the
solutions 1-4, recorded by monitoring the fluorescence at 380
nm, are presented in the inset (Figure 4). The basic features of all
the spectra look similar except of diminishing intensity with
increase of phenol concentration, and no distinct band shows up
at wavelengths longer than 300 nm that can correspond to the
7AI-phenol complex. Thus, in longer wavelength region (λ >
300 nm) the features of the excitation and absorption spectra
(Figure 2) are different, and this indicates again that the complex
is nonfluorescent.
To study the thermal effects on the excited state behavior of
the complex, we have measured the emission spectra of a mixed
solution by lowering its temperature up to -50 °C, and the
results are presented in Figure 5 (part A). The concentrations of
7AI and phenol in the mixed solution were 10-5 and 1.66
10-3
M, respectively, and the excitation wavelength was 300 nm. It is
dx.doi.org/10.1021/jp1084422 |J. Phys. Chem. A 2011, 115, 1830–1836
The Journal of Physical Chemistry A
Figure 6. Absorption spectra of a mixed solution of 7AI (10-5 M)
containing phenol of concentration 1.66
10-3 M in methylcyclohex-
ane recorded at four different temperatures in the range of 27 to -20 °C.
The inset shows the set of spectra recorded with the pure 7AI solution
(10-5 M).
seen that upon temperature lowering, the UV fluorescence of the
monomer is sharply depleted, and there is a noticeable develop-
ment of the tautomer fluorescence in the visible region. At lower
temperatures, because of higher values of the association/dimer-
ization constants, the concentrations of both 7AI2 and 7AI-
PhOH complex would be relatively larger compared to when the
solution is at room temperature. Since the light of 300 nm is
absorbed by both (7AI)2 and 7AI-PhOH complex, the observed
enhanced tautomer fluorescence at lower temperatures can be
contributed either solely by the homodimer or partly also by the
complex. To distinguish between these two possibilities, the
fluorescence spectra of pure 7AI solution (10-5 M) are also
measured by varying temperatures identically, and the results are
shown in part B in the same intensity scale. The fluorescence
excitation spectra recorded by probing the visible tautomer
fluorescence of the two solutions are shown in the respective
insets. The identical features of the two sets of FE spectra indicate
that the emitting species at 500 nm is the same under the two
conditions, and it must be the tautomeric form of the homo-
dimer. The enhancement of the tautomer fluorescence of pure
7AI solution is much larger compared to that of the mixed
solution, and this happens with much less depletion of monomer
fluorescence in the former case. At -50 °C, complete quenching
of the monomer fluorescence of the mixed solution occurs
because of formation of 7AI-PhOH complex at a large con-
centration, and the homodimer population under such condition
being comparatively low, the intensity of the tautomer fluores-
cence must be smaller. This observation supports further that the
7AI-PhOH complex is a nonemitting species.
To observe the distinct longer wavelength features of the
nonfluorescent 7AI-PhOH complex, we have measured the
absorption spectra of the same mixed solution at several low
temperature and the results are shown in Figure 6. The inset
shows the changes in absorption spectra of the pure solution of
7AI for the same effect. Thus, although the mixed solution
spectrum (trace 1) is barely different from that of pure 7AI
solution (dotted trace) at room temperature, cooling has a very
pronounced effect on concentration of the complex. The trace 4
shows that the maximum of the first band of the monomer at
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Figure 7. The changes of the fluorescence spectra of 7AI (10-5 M) in
presence of anisole at several concentrations (mentioned on the figure).
The corresponding changes of the absorption spectra are shown in the
inset.
293.5 nm is shifted to 296 nm upon complex formation, and the
longer wavelength segment of the absorption curve of the
complex is extended up to 320 nm. In contrast, the temperature
lowering to the same extent has visibly smaller effect on homo-
dimer concentration in the pure solution (inset), and it is
manifested only by increased intensity of the longer wavelength
segment of the curves beyond 300 nm. Such comparison also
indicates that at -20 °C, the homodimer population in the mixed
solution is much smaller compared to that of the complex.
To invoke a suitable model that explains quenching in the
preformed complex, we attempt first to understand whether the
hydrogen bonds of the complex have any key role to play. In the
optimized structure of the complex shown in Figure 1, the
phenolic O-H group is simultaneously a hydrogen bond donor
to the pyridinic N and acceptor for the pyrrolic N-H group.
According to the suggested mechanisms of the alcohol or acid
catalyzed complexes, the first step is likely to be a proton transfer
along N 3 3 3 H-O hydrogen bond from phenol to the excited 7AI
moiety. For a naive verification of whether such a proton transfer
is playing the role in the quenching process, we made a
comparative study of the photophysical behavior of the 1:1
complex of 7AI with anisole (methoxy benzene). In this case,
anisole is only the acceptor for the N-H 3 3 3 O hydrogen bond
between pyrrolic N-H of 7AI and oxygen atom of the methoxy
group. In Figure 7 we have presented the changes in fluorescence
spectral feature of 7AI in presence of anisole of several concen-
trations in the solutions, and the corresponding absorption
spectra are shown in the inset. It is seen that the overall
fluorescence intensity from the locally excited state of 7AI (λex
= 300 nm) is enhanced in presence of anisole. The absorption
spectra (inset) show that in the presence of anisole, the tail of the
lowest energy transition of 7AI is shifted further in the longest
wavelengths (traces 1-6). However, unlike PhOH complex no
distinct structure develops, although the concentrations of
anisole used are much larger compared to phenol. This indicates
that the hydrogen bond in 7AI-anisole complex is weaker
compared to the phenol complex, and this happens because
anisole acts only as an acceptor of a hydrogen bond. The traces 7
and 8 (dotted lines) denote that the longer wavelength tails of the
absorption spectrum of pure anisole in methylcyclohexane for
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The Journal of Physical Chemistry A
the highest and lowest concentrations used, respectively, in
recording the above-mentioned spectra of the complexes. It is
important to mention that with increase in anisole concentration,
the background absorption of the solution at 300 nm (the
wavelength selected to record the fluorescence spectra) is also
increased, and this partly contributes to the increased intensities
of the absorption traces 1-6 of the mixed solutions. However,
these increased background absorptions due to anisole hardly
contribute to the enhanced fluorescence intensity of 7AI (traces
1-6), and in support of this we have presented the emission
spectrum of pure anisole solution of the highest concentration
used (1.38
10-1 M), trace 7. It shows clearly that for excitation
at 300 nm, very little fluorescence is generated, and this certainly
cannot be responsible for the enhanced intensities of traces 1-6.
Thus, we infer that although phenol and anisole have the same
aromatic chromophore, the ability of the former for a proton/H-
atom transfer along the N 3 3 3 H-O hydrogen bond makes it an
efficient quencher of the excited electronic state of 7AI.
We suggest here two probable mechanisms for the quenching.
First, a proton-coupled electron transfer (PCET) pathway.
Following a proton transfer along N 3 3 3 H-O hydrogen bond
from phenol to excited 7AI, the produced electron-rich phen-
oxide ion should be an efficient electron donor. The occurrence
of excited state quenching of an aromatic chromophore by
phenol in 1:1 complexes in liquids have been documented in a
number of cases in the past.38-41 In a recent study, Prashanthi
and Bangal have shown that phenol can quench the fluorescence
of a pyridine-linked porphyrin derivative in dichloromethane
solution at room temperature,41 and the authors interpreted the
quenching in terms of a PCET process in the preformed 1:1
adduct of the two molecules, where the phenolic O-H binds
with the pyridinic N through a hydrogen bond. In comparison, in
the present system, the acceptor 7AI is directly excited. The
electronic excitation energy of the molecule being much higher
compared to porphyrin, the complex is in a more favorable
situation for undergoing facile PCET. According to Rehm-
Weller model,42 for facile occurrence of an electron transfer from
phenol to excited 7AI, the thermodynamic driving force, ΔG0ET,
must be negative. The lowest electronic excitation energy of 7AI
chromophore is 4.27 eV and oxidation potential of phenol is
1.47 V. Neglecting the Coulombic term (as there is no net change
in the charges in a PCET process), one estimates that for occur-
rence of the process the reduction potential of 7AI must be less
than 2.8 V. To our knowledge, this parameter for 7AI has not
been measured, although the values for a large number of other
azaaromatic compounds have been reported.43 For example, the
reduction potential of pyridine is 2.62 V, and for other sub-
stituted pyridines and most of azaaromatics the values are much
less. On the basis of such correlation, one can guess that the
reduction potential of 7AI should be smaller than that of
pyridine, and this would result in a significantly negative value
of ΔG0ET. Therefore, from a thermodynamic viewpoint, PCET in
the present system is likely to be an effective mechanism for the
occurrence of fluorescence quenching.
A proton transfer followed by an electron transfer from PhOH
to 7AI in ππ* state is effectively an H-atom transfer process. Such
a configuration has been predicted to be stable also in the
homodimer of 7AI in a recent theoretical study by Gelabert et
al.44 Using a hybrid CIS/TDDFT theoretical approach proposed
initially by Dreuw and Head-Gordon, it has been shown that
charge-transfer ππ* state of 7AI homodimer has a deep potential
energy profile with respect to a proton transfer coordinate.
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Figure 8. TDDFT calculated electronic transition energies to S1 of 7AI,
protonated 7AI (7AIHþ), phenol, and phenoxide ion (PhO-).
A photoactive ππ* excited state for the dimer has been defined
to be a configuration where a proton has been transferred from
the ππ* excited moiety to the other in the ground state. This
configuration is preferentially stabilized with respect to inter-
moiety separation on simultaneous transfer of charge from the
former to the latter moiety.
The second probable mechanism that we propose here is an
energy transfer quenching. Following light absorption by the
complex, an initial proton transfer along the N 3 3 3 H-O hydro-
gen bond leaves the system in an ion-pair state, where the
protonated 7AI is in the ππ* excited state and the anion
(phenoxide ion) in the ground state. As stated before, although
the energy transfer from excited 7AI to phenol is not energeti-
cally feasible in the neutral form, it could be facile in the said ion-
pair, and the reasons are the following. First, the excited state of
the phenoxide ion is energetically lower compared to that of the
protonated 7AI, and second, its electronic transition moment is
much higher compared to its neutral precursor.45 The energies of
the lowest excited states of 7AI, PhOH, 7AIHþ and PhO-,
predicted by electronic structure calculation at TDDFT (6-
311þG**) level is shown schematically in Figure 8. A compar-
ison of these values shows clearly that although the S1 of
protonated 7AI is below to that of 7AI, the lowest excited state
of phenoxide ion is much lower. Here, the proton transfer from
PhOH to excited 7AI and energy transfer in the other way could
also occur concertedly.
4. SUMMARY
In this paper we have shown that 7AI forms a 1:1 hydrogen-
bonded complex with phenol in a hydrocarbon solution at room
temperature. The 1:1 nature of the complex has been ascertained
by observing a linear Benesi-Hildebrand plot, and the estimated
value of the association constant is ∼120 M-1 at 25 °C.
Electronic structure calculation predicts that the complex favors
a doubly hydrogen-bonded cyclic structure. However, the hydro-
gen bonds are much weaker compared to those present in the
cyclic 1:1 complex of 7AI with acetic acid. Upon complexation,
phenol completely quenches the fluorescence of 7AI and shows
no indication of 7AI tautomerization in the excited state. On the
other hand, 7AI fluorescence in the hydrocarbon solution is
found to be enhanced upon addition of anisole, which forms a
singly hydrogen bonded (N-H 3 3 3 O) complex involving pyr-
rolic N-H group. The contrasts in photophysical behavior of the
two complexing molecules indicate that the formation of
N 3 3 3 O-H type hydrogen bond between phenol and pyidinic
N atom is the key factor for quenching of the 7AI fluorescence. As
dx.doi.org/10.1021/jp1084422 |J. Phys. Chem. A 2011, 115, 1830–1836
The Journal of Physical Chemistry A ARTICLE

a plausible mechanism, we have suggested that a PCET process (27) Hara, A.; Sakota, K.; Nakagaki, M.; Sekiya, H. Chem. Phys. Lett.
between phenol and excited 7AI is responsible for the observed 2005, 407, 30.
quenching. In the framework of Rehm-Weller model, we have (28) Brause, R.; Krugler, D.; Schmitt, M.; Kleinermanns, K.; Naka-
argued that the electron transfer from phenol to excited 7AI is an jima, A.; Miller, T. A. J. Chem. Phys. 2005, 123, 224311.
energetically favorable process (ΔG0ET < 0). We also have (29) Sakota, K.; Inoue, N.; Komoto, Y.; Sekiya, H. J. Phys. Chem. A
2007, 111, 4596.
discussed the possibility for electronic energy transfer quenching (30) Sakota, K.; Kageura, Y.; Sekiya, H. J. Chem. Phys. 2008, 129,
from the excited state of protonated 7AI to the phenoxide ion, 54303.
which is a nonfluorescent species. (31) Kageura, Y.; Sakota, K.; Sekiya, H. J. Phys. Chem. A 2009, 113,
6880.
’ AUTHOR INFORMATION (32) Koizumi, Y.; Jouvet, C.; Norihiro, T.; Ishiuchi, S.; Dedonder-
Lardeux, C.; Fujii, M. J. Chem. Phys. 2008, 129, 104311.
Corresponding Author (33) Crespo-Hern
andez, C. E.; Cohen, B.; Hare, P. M.; Kohler, B.
*Phone: þ91 33 2473 4971 (ext. 470). Fax: þ91 33 2473 2805. Chem. Rev. 2004, 104, 1977.
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(36) Sakota, K.; Jouvet, C.; Dedonder, C.; Fujii, M.; Sekiya, H. J.
’ ACKNOWLEDGMENT Phys. Chem. A 2010, 114, 11161–11166.
The authors sincerely thank the Department of Science and (37) Abe, H.; Mikami, N.; Ito, M.; Udagawa, Y. J. Phys. Chem. 1982,
Technology, Government of India for award of the Ramanna 86, 2567.
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S.K. thanks CSIR for Junior Research Fellowship. (39) Biczok, L.; Berces, T.; Linschitz, H. J. Am. Chem. Soc. 1997, 119,
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